Cu-Fe/ZrO_2-SiO_2催化苯胺、CO_2和甲醇合成苯氨基甲酸甲酯反应  

One-Pot Synthesis of Methyl N-phenyl Carbamate with Aniline, Carbon Dioxide and Methanol Catalyzed by Cu-Fe/ZrO_2-SiO_2

作　　者：李颖[1] 安华良[1] 赵新强[1] 王延吉[1] 

机构地区：[1]河北工业大学绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《高校化学工程学报》2015年第5期1271-1278,共8页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金重点项目(21476058;21236001);天津市自然科学基金(12JCYBJC12800);河北省应用基础研究计划重点基础研究(12965642D)

摘　　要：苯氨基甲酸甲酯(MPC)是非光气法合成二苯甲烷二异氰酸酯的重要中间体。以苯胺、CO2和甲醇为原料催化合成MPC是一条绿色的工艺路线。为此重点研究了制备条件对Cu-Fe/Zr O2-Si O2催化性能的影响以及反应条件对MPC合成反应的影响。结果表明,采用机械混合法制备的金属负载量为10%(按氧化物计)的Cu-Fe/Zr O2-Si O2对MPC合成反应具有较好的催化效果。对不同方法制备的催化剂进行了H2-TPR实验测定,发现催化剂表面的金属活性位越多,金属与载体之间的作用越强,催化剂的活性越好。适宜的MPC合成反应条件为:溶剂乙腈/苯胺体积比为2:1,甲醇/苯胺摩尔比为1.2:1,催化剂用量为13%(wt),CO2初压为2.0 MPa,反应温度为180℃和反应时间为11 h。在此条件下,苯胺的转化率为14.0%,MPC的收率及其选择性分别为9.2%及65.7%,远高于目前文献值。Methyl N-phenyl carbamate （MPC） is an important intermediate for the manufacture of methylene diphenyl diisoeyanate （MDI） via non-phosgene routes. A novel green process for the synthesis of MPC using aniline, carbon dioxide and methanol was studied, and the effects of preparation conditions on catalytic performance of Cu-Fe/ZrO2-SiO2 together with reaction condition effects on MPC synthesis was emphasized. The results indicate that Cu-Fe/ZrO2-SiO2 prepared by mechanical mixing with metal loading of 10%（wt） has better catalytic performance. H2-TPR results demonstrate that more metal active sites and stronger interaction between metal and support can result in better catalytic performance. The optimized reaction conditions were as follows： volume ratio of acetonitrile ： aniline =2：1, molar ratio of methanol ： aniline = 1.2：1, catalyst weight percentage =13%, CO2 initial pressure = 2.0 MPa, reaction temperature = 180~C, and reaction time = 11 h. The conversion of aniline, the yield and selectivity of MPC were 14%, 9.2% and 65.7%, respectively, which are much higher than the values reported.

关 键 词：苯胺 CO2 甲醇 负载型双金属催化剂 苯氨基甲酸甲酯 

分 类 号：TQ245.2[化学工程—有机化工]